Orientadores: Maria Helena Robert, Antonio Celso Fonseca de Arruda. / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-19T00:29:18Z (GMT). No. of bitstreams: 1 Jorge_AlexandreFonseca_D.pdf: 74832769 bytes, checksum: c12f3ee63d8a19711176184c5a9ee729 (MD5) Previous issue date: 2011 / Resumo: Este trabalho teve como objetivo estudar o processo de produção de esponjas metálicas e compósitos de baixa densidade por tixoinfiltracao. A liga metálica AA7075 foi submetida a uma analise de tixohabilidade, na qual foi observada sua adequação ao processo e foi definida a temperatura de trabalho para a infiltração. A produção das amostras consistiu em infiltrar a pasta tixotropica da liga AA7075 sobre bloqueadores removíveis (partículas de NaCl), para a produção das esponjas, e sobre bloqueadores não-removíveis de materiais cerâmicos porosos (vermiculita e cinasita), para a produção dos compósitos. Todas as esponjas metálicas e compósitos produzidos foram caracterizados quanto a sua arquitetura interna, propriedades físicas, térmicas e mecânicas. Os resultados mostraram em todos os casos uma boa qualidade geral dos produtos e uma boa repetibilidade do processo. O comportamento de todos os materiais produzidos em compressão estática ou dinâmica se mostrou próximo do comportamento típico de materiais celulares, com grande platô de deformação plástica ocorrendo com valores relativamente baixos de tensão. A analise das curvas obtidas nos ensaios de compressão semi-estática e compressão dinâmica, em conjunto com imagens de amostras parcialmente comprimidas, forneceu informações sobre os prováveis mecanismos de deformação envolvidos, incluindo o papel dos materiais de reforço. Adicionalmente, foi proposto um equacionamento para a condutividade térmica, dos compósitos, cujos resultados se mostraram satisfatoriamente correlacionados com os experimentais / Abstract: This work had the objective to study the process of production of open-cell metallic foams and low-density composites by thixoinfiltration. The AA7075 alloy underwent a thixoability analysis, in which it was observed its adequation to the process, and the working temperature for the infiltration was defined. The samples production consisted in infiltrating the thixotropic slurry of AA7075 alloy into removable space-holders (NaCl particles) for the production of the foams, and into non-removable space-holders of porous ceramic materials (vermiculite and expanded clay) for the production of the composites. All the foams and composites produced were characterized according to their internal architecture, physical, thermal, and mechanical properties. The results in all cases showed a good quality of the products in general, and a good repeatability of the process. The behavior of all the produced materials under semi-static and dynamic compression remained similar to the typical behavior of cellular materials, with a large plastic deformation plateau occurring with relatively low stress levels. The analysis of the obtained curves from the semi-static and dynamic tests, together with images from partially compressed samples, gave information about the possible deformation mechanisms involved, including the role of the reinforcement materials. Furthermore, a calculation for the thermal conductivity of the composites was proposed, with their results satisfactorily correlated to experimental data / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Orientador: Cecilia Amelia de Carvalho Zavaglia / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia mecanica / Made available in DSpace on 2018-08-04T10:23:14Z (GMT). No. of bitstreams: 1 Gomide_VivianeSilva_M.pdf: 10916166 bytes, checksum: 3d319a5e8b56700e5844bc42e9b8d18f (MD5) Previous issue date: 2005 / Resumo: Existe uma crescente demanda de materiais que possibilitam a remodelação e reconstrução de partes ósseas. A indicação de biomateriais para reconstrução dos defeitos cranianos depois do trauma, tumor ou infecção, ocorre devido a razões estéticas e proteção de estruturas intracraniais. Várias técnicas cirúrgicas vários materiais já foram utilizados na confecção dessas próteses crâniomaxilofaciais, mas é importante avaliar o comportamento desse material quanto à estabilidade fisiológica e resistência mecânica. O objetivo principal deste trabalho é desenvolver biomateriais para uso em preenchimento de defeitos ósseos. A hidroxiapatita, cerâmica bioativa semelhante à parte mineral do tecido ósseo, é um material que poderia ser utilizado para essa finalidade. Porém, essa cerâmica possui baixas tenacidade à fratura e resistência mecânica à compressão. Com a finalidade de obter materiais mais adequados para restaurações ósseas e implantes crâniomaxilofaciais, foram associadas a hidroxiapatita obtida no laboratório de materiais cerâmicos do DEMA-FEM-UNICAMP, partículas de reforço de três cerâmicas: zircônia, alumina e titânia, nas proporções de 30,40 e 50% em peso para cada composição. Os compósitos obtidos e sinterizados foram caracterizados por medida de tamanho de partículas, Microscopia Eletrônica de Varredura, Difração de Raios X e Espectroscopia de Fluorescência de Raios X e tiveram suas densidades aparentes, densidades teóricas, absorção de água, volumes aparentes e porosidades aparentes determinadas pelo ensaio de Archimedes. Algumas propriedades mecânicas como resistência à compressão, dureza e tenacidade à fratura foram determinadas. Os compósitos que tiveram melhor comportamento geral foram escolhidos para continuidade do trabalho (ensaios ¿ in vitro" e ¿Hin vivo ") / Abstract: There is a growing demand of materiaIs that make the remodeling and reconstruction of bone parts possible. Reconstruction of defects of the skulI after trauma, tumor or infection is indicated for aesthetic reasons and for protection of internal structures. Different materiaIs have been used for this purpose and alI of them must be evaluated as for their stability in physiological environments and mechanical strength. The main objective of this work is to develop biomaterials for use in fulfilIing of bone defects. The hydroxyapatite, similar bioactive ceramics to the mineral part of the tissue bone, is a material that could be used for this purpose. However, this ceramics possess decreases tenacity to the breaking and resistance mechanics the compression. With the purpose to get more adequate materiaIs for bone restorations and craniomaxilofacials implantations associates had been hydroxyapatite gotten in the laboratory of ceramic materiaIs of the DEMA-FEM-UNICAMP, particles of three ceramics bioinert, zirconia, alumina and titania, in the ratios of 30%, 40% and 50% in weight for each composition. The composites obtained and sintered were characterized by particles size measure, Scanning Electronic Microscopy, X Rays Difratometry and Spectroscopy of Fluorescence of X Rays and had its apparent densities and apparent porosity determined by the assay of Archimedes. Some mechanical properties as compressive strength, hardness and tenacity to the breaking had been performanced. The composites that had general behavior had been better chosen for continuity ofthe work (assays "in vitro" and "in vivo") / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

L'usage des matériaux composites, et en particulier des stratifiés d'unidirectionnels, ne cesse de croître dans les structures aéronautiques en raison de leur rapport masse/rigidité/résistance très intéressant. Leur utilisation s'étend désormais aux structures primaires (jusqu'ici en matériaux métalliques) des futures gammes d'avions. Dans les structures vitales de l'avion, les pièces en composites contenant des cornières composites sont de plus en plus nombreuses. Ces pièces sont soumises à des sollicitations complexes qui induisent des modes de rupture tridimensionnelle. Or, la tenue mécanique hors-plan est l'une des principales faiblesses des stratifiés d'unidirectionnels et la prévision de la tenue de structures soumises à des chargements tridimensionnelles reste actuellement un challenge scientifique. Il semble indispensable de proposer des modèles matériaux innovants offrant un degré moindre d'empirisme que les approches actuellement utilisées en bureau d'études pour le dimensionnement de structures composites mais aussi il s'avère nécessaire de proposer les procédures d'identification associées. L'objectif de cette thèse est donc de proposer une stratégie robuste pour l'analyse de la tenue de structures composites soumises à des sollicitations tridimensionnelles. Nous avons proposé une approche progressive de la rupture 3D permettant de prévoir les différents types d'endommagement et modes de ruine pouvant intervenir dans un composite stratifié. Une procédure originale d'identification des résistances hors-plan de traction et de cisaillements à partir d'essais sur cornières composites stratifiées a également été proposée. Enfin, des essais de dépliages/pliages sur cornières ont été réalisés afin valider l'approche 3D de la rupture proposée. / Composite materials, particularly unidirectional laminates, are increasingly used for the design of airplane structures because of their interesting mass/rigidity/strength ratio. Their use is now extended to the design of primaries structures (in metallic so far) for the future range of aircrafts. In those primaries structures, lots of composite components are subjected to complex out-of-plane loadings such as L-angle structures. The main failure mechanism encountered is delamination in the radius mainly due to the applied out-of-plane loadings. Nevertheless, the main weakness of the unidirectional laminates is their out-of-plane mechanical properties and the prediction of this failure mode in laminated structures (subjected to 3D loadings) remains a scientific challenge. It is thus necessary to propose an innovative 3D failure approach, physically based, and the associated identification procedure for the out-of-plane strengths. The aim of this Phd-thesis is thus to propose a 3D strength analysis method dedicated to 3D loadings and matching the requirements of a design office (low time of computation and easy to identify and to carry out). A 3D progressive failure approach which permits to predict damages and failure modes encountered in laminated structures has been proposed. The out-of-plane strengths (tensile and shears) are identified through the analysis of tests performed on L-angle structures, representative of the final aeronautical components. Finally, some unfolding/folding tests on L-angle specimens have been performed in order to validate the proposed 3D failure approach.

Les actionneurs disques sont potentiellement une solution intéressante pour des applications de transport exigeantes, comme le véhicule hybride. Mais la conception de ces actionneurs pour de telles applications se heurte à des difficultés. Une solution réside dans l’utilisation des algorithmes d’optimisations systématique. Encore faut-il disposer, pour utiliser de tels algorithmes, de modèles souples, à la fois précis et rapides. Cette thèse se focalise sur le développement de modèles analytiques fondés sur la résolution formelle des équations de Maxwell, qui permet un bon compromis entre temps de calcul et précision, à condition d’accepter certaines hypothèses simplificatrices, comme la linéarité des matériaux magnétiques. La première partie concerne les modèles électromagnétiques bi-dimensionnels, en développant la structure disque au niveau de son rayon moyen. Pour ces modèles, une attention particulière a été portée sur la modélisation des saillances aussi bien statoriques que rotoriques. Il est montré que l’approximation du coefficient de Carter permet effectivement de déterminer le couple moyen de la machine avec précision. Néanmoins, si on veut déterminer les inductions dans le fer pour calculer les pertes magnétiques, un modèle de l’encochage statorique est nécessaire. Dans un second temps, des modèles tri-dimensionnels analytiques ont été développés, afin de calculer le flux à vide de l’actionneur en prenant en compte les effets des bords et l’effet de courbure. Il est montré que la prise en compte des effets de bords est de première importance dans la modélisation des actionneurs. Par contre, une étude sur l’effet de courbure de la machine disque montre que le développement de l’actionneur au rayon moyen, pourvu que l’on utilise un modèle 3D, n’induit qu’une erreur minime. Un second point concerne l’étude des pertes magnétiques dans les matériaux composites isotropes formés de particules de fer pur isolées les unes des autres, liées puis compressées. En effet, ces matériaux sont très prometteurs en conception de machines électriques, autorisant des parcours de flux tri-dimensionnels, et une isotropie thermique, malgré leur perméabilité magnétique relativement faible. Deux matériaux de la société suédoise Hoganas (l’un dédié aux applications de machines électriques, l’autre à l’électronique de puissance, avec des grains de taille plus faible) ont été caractérisés en termes de pertes magnétiques dans une large gamme de fréquences. Un modèle de pertes classiques a été formulé, en se basant sur des observations microscopiques des échantillons de matériaux. Grâce à l’estimation de ces pertes, une procédure de séparation des pertes magnétiques a pu être mise au point. La déduction du terme de pertes excédentaires a révélé certains mécanismes de magnétisation propres à ces matériaux granulaires, dont des grains ont un comportement magnétique à priori indépendant les uns des autres. Contrairement aux matériaux laminés qui possèdent un nombre d’objets magnétiques actifs relativement bas sur la section de la tôle en champ excédentaire nul, les courants de Foucault permettant une homogénéisation du comportement magnétique lorsque la fréquence augmente, les matériaux granulaires semblent exhiber un comportement tout autre, en présentant au moins un objet magnétique actif par grain en champ excédentaire nul. De telles constatations changent la dépendance des pertes excédentaires en fonction de la fréquence (les pertes excédentaires sont alors proportionnelles à la fréquence f, alors que nous rappelons qu’elles sont proportionnelles à f^0.5 dans la plupart des matériaux laminés). Enfin un début d’optimisation a pu être mené, en se limitant aux modèles électromagnétiques bi-dimensionnels et aux matériaux laminés classiques. Diverses études de sensibilité ont été entreprises. Ce travail se termine par une analyse de l’influence d’une contrainte de puissance apparente sur la géométrie de la machine électrique. / The axial flux actuators are potentially an attractive solution for demanding automotive applications such as hybrid vehicles. However, the design of these actuators for such applications encounters some difficulties: the specifications in terms of torque and speed are complex, conflicting criteria to minimize, such as mass and losses. One solution is to use systematic optimization algorithms. To use these algorithms, flexible models are needed, both accurate and fast. This thesis focuses on developing analytical models based on the formal resolution of Maxwell's equations, which allows a good compromise between computation time and accuracy, if some simplifying assumptions such as linearity of magnetic materials are accepted. The first part concerns the electromagnetic two-dimensional models, developing the axial flux structure at its mean radius. For these models, particular attention was paid to modeling of the salience as well as the rotor stator. It is especially shown that the approximation of the Carter coefficient can effectively determine the average torque of the machine with precision. However, if we want to determine the inductions into the iron parts so as to calculate the magnetic losses, a model of stator slotting is required. In a second step, three-dimensional analytical models were developed to calculate the no-load flux in the actuator, taking into account the edges effects and the curvature effect. It is shown that taking into account the edges effects is important in the modeling of the actuators. A study on the curvature effect of the machine shows that the development of the actuator to the mean radius, provided 3D models are used, is not so wrong. A second point concerns the study of magnetic losses in isotropic composite materials, composed of particles of pure iron insulated from each other, put in a binder, and then compressed. Indeed, these materials are very promising in electric machine design, allowing three-dimensional magnetic flux paths and a thermal isotropy, despite their relatively low magnetic permeability. Two materials of the Swedish company Hoganas (one dedicated to electric machines, the other to power electronics, with grains of smaller size) were characterized in terms of magnetic losses in a wide frequency range . A classical loss model was formulated, based on microscopic observations of samples of materials. With this estimate of the classical losses component, the procedure of loss separation can be carried out. The calculation of the excess loss component revealed some specific magnetization mechanisms in these granular materials, in which grains are independent of each other. Unlike laminated materials that have a number of active magnetic objects relatively low on their section at zero field, (eddy currents allow homogenization of the magnetic behavior when the frequency increases), the granular materials appear to exhibit a totally different behavior, with at least one active magnetic object at zero excess field. This changes the dependence of excess losses as a function of frequency (the excess losses are then proportional to the frequency f, while we remember that they are proportional to f ^ 0.5 in most laminated materials). Finally a pre-optimization has been carried out, with just two-dimensional electromagnetic models, and conventional laminated materials. Various studies, as the control law, or the residual induction of the magnets, have been done. This work finishes with an analysis of the influence of a power constraint on the geometry of the electrical machine.

Les matériaux composites se caractérisent par une forte dispersion de leur durée de vie qui peut s'étendre de quelques minutes à plusieurs semaines lors d'un test de fluage. Lors d'un essai en fluage de ces matériaux nous distinguons trois phases de temps caractérisées chacune par une activité acoustique propre. Dans la première phase, le taux d'apparition des signaux d'EA est important, puis le taux diminue et atteint une valeur constante relativement faible durant la seconde phase, ensuite ce taux d'apparition s'accélère annonçant la troisième phase qui se termine par la rupture. Les caractéristiques des signaux d'émission acoustique (EA) émis dans la phase précédant la rupture sont différentes de celles des autres phases. Le premier volet de cette étude consiste à utiliser des méthodes d'apprentissage relevant de l'intelligence artificielle (réseaux de neurones, machines à vecteurs de support et classifieurs bayésiens) afin de prédire si les signaux recueillis à partir d'un matériau sous test se trouve dans la phase de pré-rupture ou non. Ce sont des méthodes qui, appliquées à l'émission acoustique, permettent d'identifier parmi un grand nombre de signaux, caractérisés par des paramètres principaux, des classes de signaux ayant des paramètres voisins et donc provenant probablement de la même phase. Ces méthodes se sont avérées très performantes en classification, nous atteignons avec les SVM une sensibilité de 82 % et une spécificité de 84% pour les résultats en validation croisée, et une sensibilité de 90 % et une spécificité de 94 % pour les résultats en test, avec un temps de calcul acceptable.Le deuxième volet de l'étude effectué dans le cadre de cette thèse concerne l'estimation de la durée de vie restante des les matériaux composites. La normalisation des courbes cumulées des signaux d'émission acoustique en fonction du temps prouve que les réponses en fluage des éprouvettes mises en test sont parfaitement ressemblantes. Un modèle a été établi pour caractériser le comportement de ce matériau lors de ce test. Deux approches sont utilisées pour déterminer le temps de rupture. Par rapport à la littérature, la première approche proposée améliore la détection des temps de transition des différentes phases. Cette approche fournit également une meilleure corrélation avec le temps de rupture. La deuxième approche est fondée sur la corrélation du temps de rupture avec le temps de référence correspondant à la diminution de la vitesse d'un certain pourcentage. Les résultats de cette dernière approche sont très intéressants : l'estimation du temps de rupture pour une éprouvette ayant une durée de vie de 1 heure peut être possible dès les 15 premières secondes, avec une erreur de l'ordre de 4 %. / The composite materials are characterized by a high dispersion of their lifetime, which may extend from several minutes to several weeks in a creep test. When tested in creep of these materials we distinguish three phases, each characterized by its own acoustic activity. In the first phase, the occurrence rate of the AE signals is important, and then the rate drops to a relatively low constant value during the second phase, then this occurrence rate accelerate announcing the third phase which ends by a rupture. The characteristics of the acoustic emission (AE) signals in the phase preceding the rupture are different from those of other phases.The first part of this study is to use learning methods from artificial intelligence (neural networks, support vector machines and Bayesian classifier) to predict if the signals collected from the material under test in the pre-rupture or not. These are methods which, when applied to acoustic emission, identify among a large number of signals, characterized by key parameters, classes of signals having similar parameters and thus probably from the same phase. These methods have proved highly effective in classification; we reach the SVM with a sensitivity of 82 % and a specificity of 84 % for cross-validation results, and a sensitivity of 90 % and a specificity of 94 % for test results, with an acceptable calculation time.The second part of the study in the framework of this thesis concerns the estimation of the remaining life of composites. Standardization of signals accumulated acoustic emission curves as a function proves that the responses of the creep test pieces are set perfectly similar. A model was developed to characterize the behavior of this material during this test. Two approaches are used to determine the time of rupture. Compared to the literature, the first proposed approach improves the detection time of transition phases. This approach also provides a better correlation with the rupture time. The second approach is based on the correlation of rupture time with the reference time corresponding to the decrease of the speed by a percentage. The results of this latter approach is very interesting : the estimation of the rupture time for a test piece having a life of one hour may be possible from the first 15 seconds, with an error of about 4 %.

Depuis les années 80, Les matériaux composites stratifié verre résine (SVR) ont été utilisés pour la construction des tuyaux et des réservoirs dans l'industrie chimique, y compris pour le stockage d’acides. Ce matériau composite présente une résistance supérieure à la corrosion. Cependant, des auteurs ont observé des ruptures accidentelles de réservoirs (horizontaux et verticaux) contenant des acides (chlorhydrique et sulfurique). Ces ruptures sont attribuées au mécanisme de corrosion sous contrainte (CSC). La corrosion des fibres de verre dans une solution acide est moins connue mais reste très importante. Ce mécanisme de corrosion, appelée désalcalinisation de la fibre peut provoquer la fissuration de la fibre de verre.Des essais de corrosion avec de l’acide chlorhydrique (37%) ont été effectués sur éprouvette SVR. Ces essais de corrosion ont été suivis par émission acoustique. Les observations au microscope électroniques à balayage (MEB) et les analyses physico-chimiques confirment la corrosion de fibres de verre dans une solution de HCl. L’utilisation de la micro-tomographie nous montre que cette technique permet d’avoir une information sur la profondeur d’attaque du matériau.Une approche statistique est utilisée pour caractériser les paramètres de la salve d’émission acoustique afin de les séparer. Le Clustering est fait en utilisant la méthode des k-moyennes. Trois classes d’émission acoustique distinctes ont ainsi été identifiées. L’analyse croisée de l’émission acoustique et des observations ont permis de relier les classes observées aux conséquences de la corrosion du SVR. / Since the 1980, Glass Reinforced Plastic (GRP) has been used for construction of pipes and tanks in the chemical industry, including the storage of mineral acids. This composite material offers superior and cost effective corrosion resistance. However, authors found accidental breakage of tanks (horizontal and vertical) containing mineral acids (hydrochloric and sulphuric). These failures are attributed to environmental stress-corrosion cracking (ESCC) mechanism. The corrosion of glass fibers in mineral acid solution is less known but very important. The mechanism of the corrosion, called leaching, is thought to induce tensile stresses in the surface of the glass. These stresses could be large enough to cause cracking of the fiber glass.Corrosion tests have been performed on GRP specimen. Aggressive environments used are hydrochloric acid (37%) This environment is known to react with E-glass. Corrosion tests have been monitored by acoustic emission.SEM observations and physicochemical analysis confirm the corrosion of glass fibers in HCl solution. The use of micro - tomography allows to have information on the depth of degradation of the material.Statistical approaches are used to characterize hit’s parameters. Clustering is made by using k-mean’s method. Three distinct acoustic emission classes are identified. Thanks to SEM observations and acoustic emission results, clusters can be assigned to the appearance of minor defects in the material.

Hybrid composites forms an important field of research in the area of composite science and engineering as it gives the advantage of avoiding complex lay-up designs and provides better tuning compatibility to get desired properties in comparison with their mono-fiber counterpart. Further, utilization of composites for low temperature structures has been hindered by inconsistency of material property data and not much is reported on thermal characteristics of hybrid composites at cryogenic temperatures. This research work is focused on development of carbon-glass epoxy hybrid composite and to study the thermal behavior of these materials in comparison to its mono-fiber counterparts especially at cryogenic temperatures. The objectives are classified into the following three parts: Development of a hybrid composite with urethane modified epoxy matrix system (toughening agent used is Propyltrimethoxysilane (PTMO) and Toluene Di-Isocyanate (TDI) is added to get the polyurethane structure), for cryogenic applications. Study and understand the limitations and complexities of the experimental methodologies involved in evaluating the thermal properties of these materials namely thermal conductivity, coefficient of thermal expansion and specific heat. Finally to look into the appropriate theoretical calculations and experimental results to understand the variations, if any, for these materials. Specifically the following contributions are reported in this thesis: Evaluated the modified matrix system for its physical and mechanical properties at 20K. Specimens were prepared with D638 ASTM standard, modified to suit pin loading configuration in the cryostat/Instron machine. After assessing the suitability of the matrix system, mono fibre composites of different types were made and evaluated their thermal properties viz, coefficient of thermal expansion, thermal conductivity and specific heat down to 20K. Based on the results of the above, a hybrid composite configuration was evolved which exhibits optimal thermal characteristics at low temperatures and its characterization for various thermal properties at cryogenic temperatures was carried out. Comparisons of the experimental results were made with macro-mechanical model and micro-mechanical model (rule of mixtures) of composite materials. The present work throws light to the fact that hybrid polymer matrix composites can very well be considered for cryogenic applications where the combination or trade off between properties like strength to conductivity ratio, modulus to conductivity ratio and low cost is to be made. The mechanical properties of hybrid composites also need to be studied to complement the study on thermal properties reported in this thesis. It is essential to have a complete understanding of behaviour of these materials at cryogenic temperatures with respect to both thermal and mechanical properties as it is evident from the available literature that the emerging demands are multi-disciplinary in nature. The present research work is aimed at highlighting the use of hybrid composites to achieve the desirable thermal properties and thereby inviting the attention of scientists and engineers who are engaged in the design of cost effective structures and appliances for cryogenic environments to focus on further research to develop

Chapter 1. A Brief Overview of Low Molecular Mass Gels and their Applications This chapter deals with molecular gels derived from the self-assembly of small organic molecules (typical molecular weight < 2000 daltons), endowed with appropriate functions to promote anisotropic growth of supramolecular aggregates, by means of various non-covalent interactions like van der Waals, π-πstacking, H-bonding etc., leading to a self-assembled fibrillar network (SAFIN). Several representative examples from the literature (Chart 1) are discussed to demonstrate the structural diversity of the gelator molecules which form self-assembled organogels or hydrogels. Chart 1 Besides emphasizing on the diverse molecular structures of the gelators, applications of gel phase materials as functional nanostructures are also discussed (Scheme 1). Some of the aspects that have been elaborated in this context include the use of gels as reaction media, as sensors, in light harvesting, as biomaterials and in optoelectronic applications. Scheme 1 Chapter 2. Supramolecular Chirality in Organogels: Spectroscopic, Morphological and Rheological Investigations of Gels/Xerogels derived from Alkyl Pyrenyl Urethanes This chapter addresses the formation of chiral supramolecular structures in the organogels derived from chiral 1R (or 2R), and its mixture with its enantiomer (1S) and a series of achiral analogues (3-9) by extensive circular dichroism (CD) spectroscopic measurements (Chart 2). Morphological studies by atomic force microscopy (AFM) and scanning electron microscopy (SEM) were complemented by the measurements of their bulk properties by thermal stability and rheological studies. Specific molecular recognition events (1/3 vs 2/3) and solvent effects (isooctane vs dodecane) were found to be critical in the formation of the chiral aggregates. Computational studies were carried out to understand the interactions responsible for the formation of chiral superstructures. Chapter 3. Self-assembled Composite Organogels based on a Thermo-reversible Photoactive n-Acene Fibrillar Scaffold and Organic Ligand stabilized ZnO Nanoparticles Organic/inorganic composite organogels were obtained in n-BuOH by the self-assembly of 2,3-di-n-decyloxyanthracene (DDOA, Chart 3) in this solvent in the presence of ZnO nanoparticles (NPs) capped with different organic ligands (Chart 4). When ligands (oleic acid or 2,3-substituted anthracenic acid/oleic acid mixed shell) having structural similarity with the gelator molecule were used to cap the NPs, a homogeneous dispersion of the NPs in the gel matrix was obtained, as confirmed by microscopy (TEM and confocal fluorescence microscopy) experiments. The efficient integration of these NPs into the gel fibers resulted in a significant quenching (20-25%) of DDOA emission, even with extremely small loading of these NPs (~ 10-4mol% compared to DDOA) into the gel fibers. The mechanical properties (rheology were unaffected relative to the pristine DDOA organogel. However, the presence of the NPs lowered the critical gelation concentration and accelerated the gelation kinetics. Attempts to disperse these NPs (the ones without fluoro capping) on the aerogel fibers of DDOA by dissolving both DDOA and the NPs in supercritical (sc) CO2 were not successful (Fig. 1), since the NPs could not be dissolved in scCO2. Figure 1. (a) TEM images of DDOA aerogels obtained from scCO2, containing A23-NPs, scale bar 200 nm; (b) SEM image of DDOA aerogel obtained in the presence of OL-NPs, scale bar 10 µm. Chapter 4. Donor-Acdeptor Interaction Promoted Gelation Of Organic Fluids by Anthracene Carboxamides/2,4,7-Trinitrofluorenone Tris Carboxamides of anthracene were found to form charge-transfer driven organogels in a range of aliphatic alcohols in the presence of an equivalent of (electron-deficient) 2,4,7-trinitrofluorenone (TNF) (Chart 5). Intense color developed in the gel state during the sol to gel phase transition process (Fig 2) Besides, none of these carboxamides were able to form gel in the absence of TNF, suggesting the importance of charge-transfer interaction in the gel formation. Importantly, most of these gels formed only through rapid cooling of the hot solution, otherwise, leading to the precipitation of the CT complex from the solvent. This result indicated that the kinetics is very important for the formation of these gels. Optimum stoichiometry of the donor and acceptor was found to be 1:1. At this molar ratio of the donor and the acceptor, the gels not only showed the highest thermal stability (thermal gel melting experiments), they also displayed the highest values of the mechanical strength and the yield stress (rheology experiments). All the gels showed extensive quenching of the emission of the monomeric anthracenic donor. For the gels derived from the 2-substituted donor, a low energy emission at high wavelength indicated the formation of an emissive CT exciplex. X-ray powder diffraction studies of these xerogels revealed the presence of layered, fibrillar structures in the xerogel phase. (For structural formula pl see the abstract file)

Les composites stratifiés de plis unidirectionnels en carbone/époxy sont fortement utilisés pour alléger les structures aéronautiques tout en conservant de bonnes propriétés structurales. Toutefois, les avantages de ce type de matériau ne sont pas encore pleinement exploités de par le manque de confiance accordée aux modèles de prévision de l’endommagement, dont notamment ceux concernant le délaminage. C’est pourquoi l’objectif de cette thèse était de développer une stratégie de modélisation du délaminage adaptée aux structures composites stratifiées. Cette stratégie s’est appuyée sur le développement d’un modèle de zone cohésive prenant en compte les ingrédients nécessaires à la bonne description de l’amorçage et de la propagation de la fissure : (i) un critère d’amorçage avec un renforcement en compression/cisaillement hors-plan, (ii) une loi de propagation décrivant l’évolution de la ténacité en fonction de la mixité de mode et (iii) la prise en compte du couplage inter/intralaminaire. Pour identifier ce nouveau modèle, une procédure d’identification efficace, s’appuyant sur un essai de traction sur plaque rainurée, a été mise en place. Cette procédure d’identification a permis de démontrer que la ténacité semble indépendante (i) de l’orientation des plis adjacents à l’interface et (ii) de l’empilement étudié. De même, pour décrire l’évolution de la ténacité, une nouvelle loi de propagation adaptée au matériau carbone/époxy a été proposée. Pour finir, la stratégie de modélisation, complétée par une stratégie de calcul, a été appliquée sur différents cas structuraux pour mettre en avant ses apports et ses premières limites. / The carbon/epoxy laminated composites of unidirectional plies are strongly used in order to reduce the weight of aeronautical structures while at the same time proposing good structural properties. However, the advantages of this kind of material are not fully exploited due to the lack of confidence in damage models, like ones concerning delamination. Then, the purpose of this work was the development of a strategy to model delamination in laminated composite structures. This strategy was based on the development of a cohesive zone model taking into account the ingredients necessary to the well description of the onset of delamination and the crack growth: (i) an onset criterion with an out-of-plan compression/shearing reinforcement, (ii) a propagation law describing the evolution of the fracture toughness as a function of mixed mode ratio and (iii) the inter/intralaminar coupling. To identify this new model, an efficient identification procedure, basing on a tensile test on notched specimen, has been proposed. This identification procedure has demonstrated that the fracture toughness seems to be independent of (i) the orientation of plies closed to the interface and (ii) the stacking sequence. Furthermore, to describe the evolution of the fracture toughness, a new propagation law adapted to carbon/epoxy material has been proposed. Finally, the strategy to model delamination, completed by a calculation strategy, has been applied on several structural cases to prove its contributions and its first limitations.

Orientador: Paulo Sollero / Tese (doutorado) - Universidade Estaudal de Campinas. Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-07T18:05:59Z (GMT). No. of bitstreams: 1 Paiva_WilliamPortilhode_D.pdf: 26643195 bytes, checksum: 744132c2c47025a4ed4eec9de86c860b (MD5) Previous issue date: 2005 / Resumo: Esta tese apresenta o desenvolvimento, a implementação e aplicações de uma formulação de elementos de contorno para análise de problemas estáticos e dinâmicos em placas anisotrópicas submetidas a carregamentos de flexão. O trabalho se baseia na teoria de placas finas de Kirchhoff Uma vez que a formulação dinâmica de elementos de contorno não foi encontrada na literatura consultada, as análises são realizadas utilizando-se uma formulação desenvolvida a partir das soluções fundamentais para elastostática. As integrais de domínio, provenientes dos carregamentos distribuídos ou dos termos de inércia, são transformadas em integrais de contorno usando-se o método da reciprocidade dual. Esta formulação é aplicada no cálculo da deflexão de placas isotrópicas e anisotrópicas, na análise dinâmica de estruturas ortotrópicas, anisotrópicas e estruturas de materiais compósitos laminados, submetidas a cargas harmônicas. É analisada a influência dos nós internos e da malha na precisão dos resultados. Os resultados numéricos são apresentados para problemas quaseisotrópicos, ortotrópicos e totalmente anisotrópicos. Os resultados obtidos são comparados com resultados presentes na literatura e mostram boa concordância / Abstract: Here, static and dynamic analysis of a number of anisotropic problems using the boundary element method are presented. The formulation used is developed fram the elastostatic fundamental solutions and the domain integraIs due to inertial terms are transformed into boundary integraIs by using the dual recipracity method. Application is made to the calculation of deflections in anisotrapic plates, to the dynamic analysis of orthotrapic plates and to the analysis of anisotropic and composite laminar plates under harmonic loads. Numerical results are presented for quasi-isotropic, orthotropic and anisotrapic problems. The influence of number of internal nodes and number of boundary elements on the accuracy of the results is analyzed. The results are compared with other results fram the literature showing good agreement / Doutorado / Mecanica dos Sólidos e Projeto Mecanico / Doutor em Engenharia Mecânica